Characterization and Formation of Particulate Nitrate in a Coastal Area

Particulate nitrates play important roles in the atmosphere. They consist mainly of NH4NO3 and NaNO3, products from the reactions of gaseous HNO3 with gaseous NH3 and sea salt, respectively. The gas-to-particle phase conversion of nitrate changes its deposition characteristics and ultimately changes the transport and deposition rates of the locally produced species. Studies were conducted to develop background information on the particle concentrations and size distributions and the chemistry and kinetics behind the interactions. The predominant nitrate species in the Tampa Bay area was identified as coarse mode NaNO3. NH4NO3 was not detected as it has high volatility at ambient temperatures. Spatial distribution sampling determined a gradient of NaCl and NaNO3 with increased distance from the coastal shore and an increase in the gas-to-particle conversion of nitric acid along a predominant air mass trajectory. The EQUISOLV II thermodynamic equilibrium model was evaluated. It was determined that the model can be used to predict gas and size-distributed particulate matter concentrations. The model was also used to examine the gas-to-particle partitioning of nitric acid to nitrate by NaCl and CaCO3. Both sodium and calcium partitioned nitrate to the particle phase. The magnitude of the partitioning was directly dependent on the equilibrium coefficients. The fine mode percentage of the total nitrate was determined using two methods. The results were used to expand the current data set to account for the coarse mode nitrate, and they indicated that particle nitrate accounted for 9% of the total nitrogen deposition flux to Tampa Bay. The formation of particle nitrate was examined using a nitrate accumulation model. Results indicated that the equilibrium time for particles less than 10 um in diameter was significantly less than their atmospheric residence time, with fastest conversion occurring under the highest relative humidity conditions. This information is vital in the development of atmospheric nitrogen dry deposition estimates, which are used to assess water quality and nutrient loading. These data can be used to determine air-monitoring strategies and to develop models that account for the coarse particle nitrogen species